Process for manufacture of phosphoric acid



Nov. 28, 1950 B'. w. HAMMAREN Erm. 2,531,977

PROCESS FOR MANUFACTURE OF PHOSPHORIC ACID FiledJan. 22, 1948 2 Sheets-Sheet 1 Nov. 28, 1950 B. w. HAMMAREN ETAL 2,531,977

PROCESS FR MANUFACTURE OF' PHOSPHORIC ACID 2 Sheets-Sheet 2 Filed Jap. 22, 1948 INVENTORS BERNDT WALDEMAR HAMMAREN ROBERT VOSE TOWNEND ATTORNEY.

a" 'new and imprcved'nroce `to `about 35% H3P04. .Furtheririorej l y n lmowledge, no prior process'has producedstr n'g phosphoric acid with the conconiitaiitproduction `of a high quality calcium sulfatesanliydrite;`

`ducing increased yields of `strong phosphoric Vthe invention` is o the more conipleteutilizati .thereagents used in the process. lurther;o

Patented Nov. 28, 1950 vmoccss non MANUIMC'Py jPHOSIfHORIC ACID Berndt Waldemar Hammaren, Floral Bark, N. Y.,

' andR'obert/ Vose'lipwnend, Arlington, N. J2, as-

signo'r's'to Alld Chemical & Dye'Corporation, NewYork, N'.Y.,"a corporatonzof N ew York o Anaiatfiaiiiiy 22, we, Serie .3,784

l? Claims.

1 A u v This invention relates to ,the pro Awnln'osphoric acid Iand more pa phosphate rock foto Sirone phcsphlrlc'acd with nl@ @gneomijtii ,production of 'im @ved calcur sulfatl `lnfthe conventional "W et. rnethod ,orf `p1 l `zliucing phosphoric acid,'phosphaterocli yis digest th .a inixture of phosphoricilacidhand s ,uliuric` -4acid, causing a reaction between thecalciuin phosphate inthe rock and the sulfurifacid jftoproduce `phosphoric acid and a precipitate" ofhydrate'd calcium sulfate. Itlis Wellknownin thev artlt "at due to the'set'tling or `filtration'ld'iiiifzulties the calcium sulfate produced .lo

phosphate rock withsulfuricacidgth'e stren hof the phosphoric acid so produced is` usually aiprocess 4for economically'and "eiiicientl'y fprod. Strong phosphoric acid referred itc.; hereinislA id assaying over 35% HsPOi.' Another object 'of this invention is the )production L,of ,a` purified calcium sulfate anhydrite. A further objectrof One object oiA the present invention isto'provige and advantages will .be Lapparentfr'om scription and accompanying drawings.

`.The `present inventionfcoinprises `digesting phosphate rock instrong'` phosphoric a monocalcium phosphatedissolved,in ev phoric acid, separating'the coarse gan ueafd other insoluble materials rointhe liquor,

sulfuric acid tothe liquor` to, gerierate" phosph separating phosphoric acid solution".froiri` the calcium sulfate by filtration, tiaung thecaiium sulfate precipitate with strongsulfuric" aci'dto sulfate anhydrite. The sulfuricacidwhichyvas used for treating the calcium, su,lfate,"after separation and containingrecovered soluble phosphates is utilizedin the process-for, converting the xnonocalciumy phosphliate.y lto phosph and precipitating calcium sulfate. ELilgeyvi'sea .portion of the phosphoric' acid p` oducedxinrthe process is recirculatedfor.thepurppse o igesting and converting the phosphate rpckgtohrnono- Calcium phosphate.

faiaing ciega-figues `5 phoric acid and calciumsulfate Without rst`sep`4 'i Wehavf'fundthat,calcium sulfate precipitates produced 'iricoiive'n'tional practice" contain phospirates "in an'insoluble'fori', kresulting`in` a `loss fupto or onore phosphoric acid.` "We are ujabie to `account fof'thefnondigestion of'such p sphates when treated with sulfuric acid iii the al'stages of ithe process.` `We havmade "the u A* sing discovery that" sulfuric acidi'of the proper concentration Whenadded to the calcium siiliatevprecipitate maintained at the desired tem* I 'perat'ure jperiorins at leasti two `functions; (d)

(lnv'e1jting'-i: Ktlie' insoluble 'phosphate'dn the 'precipitate tol soluble` phosphates Whichfcan 'be readily Arecovered in the process, therebyeijh "ng ythe` ;fi`e'l ;lsof phosphoricacid; :and 3`(b) storming Luie paiciuiillsifate hydrate ito ciunrsulfatearihdrit'e which isleasil'y fi ni t" e 'solution-'VWithout blinding' *the M eatrrientofhydrated calciumsulfate produced ingtlie processvvith sulfuric acid has`tlie AIfurtherfadvantagesf:of purifying the Acalcium `l 'vof'v'eliiniwating yth'efrequirerncrrtf'of 'i ther k treat/Ir;ent of Qthe hydrate to #convert lit ,'rriasulfulic @bid censure@ in .treating Calcium sulfate j nycrat arejcipitatefis smaujin anit fand dior nreconony and4 eiiicie'ncy V-the l in iggturedof actedV sulfuric acid and'r soluble fphosph n tes j resulting from such treatment faire tonjthe frear'ztor for further c'oiiversiohof x'th'e iiionooal s ruin phosphate into phosphoiic'iacid. in this manner therelis 'accomplished not only" a K"complete utilization of the sulfuric "acidbut also thefavoidanc'e of a 'waste 'acid disposal problem. By returning the solubleifphosphates tothereactonintheAsystem `these lphosphates are recovered as strong phosphoric jacid- Without the i I zecessitryj4 of employing `a separate expensive apparatus-fonte?? recovery i' Pnotherieature `ofthe `present invention inslsepar ion ofthe inonooalciuinfphosphate lsolution resulting from the `digesltion'of phosphate rock .withmstron'g phosphoric 'acid to "recieve and jtlier insoluble Hrntaterial, lt''herlcy eliminating these impurities ^i`ro`in` the ca H1 suliatesub'sequently precipitated in ,the proess hy l tionv of suliuricacid. "flvhisiiiakeslnl 55., statistics. eccoci@isaiasi."ifif classification of the dry ground calcium sulfate is practiced, greatly lessens the olassication load on the milling system, thereby markedly reducing the cost of processing calcium sulfate as well as eiecting an improved product.

Removal of t e gangue and other insoluble material from the monocalcium sphate solution prior to reaction v .th su'iiur c also avoids carrying over such materials into the phosphoric acid and resuits in a purer phosphoric duced into digester i, wherein the rock is dis-` solved in an excess of strong phosphoric acid to produce a monocalcium phosphate solution. rihe phosphate roch prior to introduction into the system is first ground to requisite degree oi nneness, preferably so that all material passes a meshscreen.

Phosphate rock, after grinding, may be used as a charging material to the process without any preliminary treatment. However, we have found that improved results were obtained by feeding the rook into a rotary calciner and heating it in direct contact with hot combustion gases at a temperature oi about 1450" F. for the purpose oi destroying the organic compounds. in this manner some of the impurities naturally present in phosphate rook are removed or reduced in amount, thereby resulting in a ore highly puri-- ed phosphoric acid and calcium sulfate produced from the process. The calcined rock may then be ground to the desired degree of 'dneness.

Strong phosphoric acid previously produced in the process is introduced into the digester through conduit 2, in an amount in excess of that required to convert the phosphate roch to monocalcium phosphate and to impart sufficient iiuidity to the reaction mixture to eiectuate ready separation of the gangue from the liquor. Preferably, 8 to le parts by Weight of phosphoric acid solution are added to l part by weight of pho.,- phate rock. Generally, itwill be found desir able to recirculate a greater quantity of phosphoric acid for digestion or" the phosphate rock when producing a more concentrated acid as an end product; for example, when operating the process for 53h04, the ratio by Weight of recirculated phosphoric acid to phosphate roel; or" about 10:1 will give good results; for 55% HsPOi, a ratio of 11:1; for 60% Helln, a ratio of 12:1; and for 65% l-Isl'Oi, a ratio of 14:1. l the process is carried out Without the step of ltering the gangue as illustrated in Fig. 2, an even lower ratio of phosphoric acid to phosphate roclr may be employed. Moderate temperatures oi the order to 70 to 80 C., preferably 75 C., and the short time of less than two hours, preferably approximately one hour, will cause dissolution of the phosphate rock to monocalcium phosphate.

Although one digester is shown in the drawing, two digesters connected in series are preferred. These digesters may be of conventional design. Y

The effluent of digester i is then passed to classifier or filter 3 for more or less complete separation of gangue and insoluble material particularly of coarse solids from the monocalciuri phosphate liquor. Any suitable separating device may be used for this purpose. The separated gangue is water-washed to remove soluble phosphates adhering thereto, and the waterwashings are combined with the separated monocaloium phosphate liquor and the mixture introduced into reactor d.

A solution of sulfuric acid and phosphoric obtained from the treatment of the hydrated calcium sulfate in the process directed through line i3 into mixing tank and to the latter from an external source is added, as required, suliu ic acid, which may be 93% commercial acid. luixing tank 5 serves as a vessel for comming-ling the solution of sulfuric and phosphoric acids with added sulfuric acid to maintain therein the desired amount and `concentration of sulfuric acid and also as a surge tank from which regulated amounts of acid are fed from mixing tank 5 into reactor Il. Good conversion of mono calci in phosphate to phosphoric acid is obtained with sulfuric acid varying in concentration fr m 25 to 35%, preferably about 30%. The phosphoric acid in mixing tank 5 acts as a diluent and facilitates the separation of calcium sulfate from the liquor. sulfuric acid in slight excess oi the amount theoretically required to convert all the monocalcium phosphate of phosphoric acid is added to reactor il, thereby avod." g wasting acid and obtaining a phosphoric acid requiring a minimum of purification to remove surplus sulfuric acid. We have found satisfactory results were obtained when the free sulfuric acid content in the phosphoric acid product was between 0.15% and 1.0%.

Suliuric acid reacts with the monocalciuin phosphate in reactor l to produce ic acid and a precipitate consisting of hy rated ciurn` sulfate at realtively mild conditions, ranging om temperatures oi approximately 50 to C., preferably 60 C. for 50% and 55% HaPOf.. and 75 C. for 60% and 65% acid, and a time of about one-half to two hours, preferably one hour. rihe reactor may be of conventional design and preferably two reactors in series are employed.

lThe phosphoric acid solution and precipitated calcium sulfate then pass from reactor l into 'filter G for separation of the solid calcium sulfate from the phosphoric acid. One important advantage of this process is that good separation between solid and liquid need not be obtained. As previously explained, it is diiicult to sharply sparate the solid hydrated calcium sulfate from the liquor. Since in this process it is not necessary to obtain a dry solid from the liquor, the hydrated calcium sulfate may be removed in a wet form containing substantial amounts of phosphoric acid. This latter phosphoric acid is recirculated in the process in admiature with sulfuric acid for which it serves as a di tient and subsequently recovered.

Separated phosphoric acid is withdrawn from lter ii through conduit 'i and a portion or it released irom the systemthrough line t as a product or" the process. Iihe remaining prosphorc acid is recirculated, the major portion returning to digester l through lines i and 2 to convert the phosphate rock into monocalcium phosphate, and the smaller amount introduced through line t into filter 3 as an additional means of was ing the gangue free from soluble phosphates and 'unreacted calcium phosphate.

Calcium sulfate 4hydrate and phosphoric acid "iiows from iilter 6 into converter I I into which o Time, Per Cent, Per Cent, Calcium Temperature C hours. Haro; Hiso. Y sulfate 20 5-28 5-20 Gypsumt 2-3 5-28 133 Anhydrite. 2-3 5-28 128s30 D0. 2-3 5-28 120 Do. 2-3 5-28 115 Do.

1These concentrations are approximately the minimum :itohe temperatures indicated for stable anhydrite forma- For production of strong phosphoric acid of 35% or higher concentration, we prefer to treat the calcium sulfate hydrate with sulfuric acid solutions of at least 28% HzSO4 concentration,

Eliiuent from converter II is then introduced into filter I2 for the purpose of separating calcium sulfate anhydrite from the liquor. Very small amounts of sulfuric acid are consumed in converter I I, the primary effect being one of dilution by the water of hydration. The filtrate from lter I2, containing unreacted sulfuric acid and phosphoric acid is returned through line I3 to mixing tank 5 and thence into reactor 4 to effect conversion of monocalcium phosphate to phosphoric acid and precipitation of calcium sulfate. In this manner all of the sulfuric acid introduced into the process is usefully employed. If a classifier is used instead of iilter 3 for handling the gangue, a clarifying filter s-hould desirably be interposed in return line I3 to remove the solids in the liquid flowing therethrough.

A portion of the filtrate from filter I2 is returned through line I to converter II for the purpose of diluting the mixture and providing a uid mix which will readily flow to filter I2 and be easily separated therein. Calcium sulfate anhydrite is washed with water to remove soluble materials therefrom and the water washings combined with the filtrate.

Insoluble calcium sulfate anhydrite when removed from iilter I2 is in a moist state and should desirably be heated to a temperature of about 800 C. in calciner I4 within 2 to 3 hours after filtration. Calcined calcium sulfate anhydrite is then cooled in cooler I by` simply blowing` cold air through the hot Calcined product and the cooled calcium sulfate disintegrated to break up agglomerates in disintegrator I6 and thence removed from the system for packaging and shipping. f

Calcium sulfate anhydrite may be readily obtained in a particle size down to 2 to 3 microns by introducing calcium sulfate anhydrite seed in converter I I of Fig. 1 or converter 24 of Fig. 2. Anhydrite seed, for example, may be conveniently prepared from the filter-cake solids fromllter 6 or filter 23 by digesting them with two parts by weight strong sulfuric acid, preferably with acid having a concentration of 85% or higher sulfurie acid, at about 55 C. for one-half hour or longer. Amounts of seed between 2% and 10% of the weight of the hydrated calcium sulfate to be treated were found to be effective. When iiitering off the gangue in accordance with the operation illustrated in Fig. 1, a remarkable White and brilliant anhydrite can be obtained' which is especially suitable and desirable for use as a paper iiller or pigmentextender.

Fig. 2 represents an alternative simplified method of practicing the invention. Calcined phosphate; rock together with recirculated phosphoric acid from line 2'I are introduced into digester 2| for the purpose of converting the rock into :monocalcium phosphate. 'I'he effluent from digester 2I without separation of the gangue, is directed into reactor 22, wherein it is mixed with sulfuric acid recovered from the processV by way of` line 28 andthe monocalcium phosphate converted to phosphoric acid and a precipitate of calcium sulfate. If this supply of sulfuric acid is insufficient for conversion of the mono-calcium phosphate, supplemental acid from an external source may bev introduced into reactor 22. The mixture of phosphoric acid and calcium sulfate is passed into filter 23 to separate the solids therefrom. The iiltrate, consisting of strong phosphoric acid, is in small part removed from the system through line 29 as an end product, and the greater portion recirculated through line 2'I t0 the digester for further digestion of phosphate rock. The precipitate from filter 23` is introduced into converter 24 and admixed therein with sulfuric acid, whereby the insoluble phosphates are acted upon by the acid to form soluble phosphates and the calcium sulfate hydrate is transformed to calcium sulfate anhydrite.

The reaction products of converter 24 are separated by filter 25 into a solid consisting primarily of calcium sulfate anhydrite and filtrate composed of a mixture of sulfuric acid and phosphoric acid. This latter mixture is returned through line` 28 to reactor 22 to effect conversion of the monocalcium phosphate to phosphoric acid and calcium sulfate. If lter 25 does` not remove the solids completely but is operated in such manner that a small amount of semi-colloidal matter is carried through, the solids in the filtrate may be removed by a clarifying iilter interposed in line 28. A portion of the iiltrate from filter 25 may be returned through conduit 32 to converter 24. Calcium sulfate anhydrite is washed with water to remove soluble compounds adhering thereto and the water washings combined with the filtrate. Gangue may be separated from the calcium sulfate anhydrite by any suitable classification procedure. Although not shown in the drawings, surge tanks may be in'- terposed at various points in the systems illustrated in Figures 1 and 2 for the purpose of assuring more constant flow of the materials sheet shown in Fig. 1 to produce 50 55%, 60%' and 65% phosphoric acid, respectively. Table 2, columns V and VI, records the data for operations in accordance with Fig. 2 when producing 50% and 60% phosphoric acid, respectively.`

' Table 1 I II III IV Calcined Phosphate Rock charged to digester.---pounds.- 2, 200 2, 200 2, 160 2, 140 P205 in cal'cined Phosphate Rock..- 748 746 746 746 Phosphoric digester -pounds-. 20, 000 22, 000 24, O 30, 000 Digester temperature. --C-. 75 75 75 Digester time hours-- 1 1 1 S/t Effluent leaving digester and entering filter -pounds-- 22, 200 24, 200 26, 160 32, 140 Phosphoric acid recirculated to Y filter pounds.. 1, 000 1, 000 1, O00 1, 000 Water for Washing gangue 500 500 360 300 Gangue removed from filter pounds.. 800 800 720 80() Composition of gangue: Y Solids --do-.-- 460 470 428 50o 340 330 292 300 140 140 140 144 20 16 16 16 P205 loss in gangue-----percent-. 2. 7 2.1 2. 1 2. 1 Filtrate` (monooalcium phosphate solution) leaving filter and entering reactor. .pounds.- 22, 900 24, 900 26, 800 32, 640 Sulfuric acid entering reactor pounds.. 300 218 546 638 Concentration of sulfuric acid per cent.- 93. 33 93.57 93. 41 93. 10 Recirculated acid (I-IzSOi and H3PO4) entering reactor pounds.. 4, 800 5, 700 4, 320 4, 260 Reactor temperature --C 60 60 5 75 75 Reactor time hours.- 2 2 2 te Effluent leaving reactor and entering ltcr .pounds.- 28,000 30,818 31, 666 37, 538 Phosphoric acid product leavmg Y system.. .pounds.. 2,000 1, 818 l, 666 v1, 538 d0 890 700 560 460 ca 724 724 724 724 Analysis of phosphoric acid product:

IYI3PO4 per cent-- Y 50 55 60 65 H O4 -d0 0. 5 O. 55 0. 6 0. 65 Slurry lleaving filter and enteringr Y converter .pounds-- 5, 000 6, 000 5, 000 5, 600 Solids in slurry. d0-... 3, 000 3, 000 sulfuric acid entering converter Y pounds.. 1, 600 1, 700 1, 400 1, 340 Concentration oi sulfuric acid Y l Y per cent-. 93. 13 93.17 93. 14 93.14 Filtrate entering converter from Y subsequent filtration-.poun ls.. 3, 000 3, 300 3, 300 3, 400 Effluent leaving converter and entering filter pounds.. 9, G00 11, 000 9, 700 9, 740 Water for washing calcium sulfate l anhydrite.... ".-pounds-- 1, 400 1,300 1, 260 1, 260 Precipitato removed from filter pounds-. 3, 200 3, 300 3, 340 3, 340 Composition of precipitate:

Solids -.do 2, 400 2, 400 2, 440 2, 426 CaSO4 in solids -do 2, 300 2, 360 2, 400 H2 l 800 900 900 936 P205.- -.do 4 i 6 6 6 P205 loss in calcium sulfate anhydrite per cent.- 0. 5 0.8 0.8 0.8 Calcium sulfate anhydrit'e after calcination, cooling and disintegrating. pounds.. 2, 340 Calcium sulfate content.. .do.- 2, 328

Table 2 V VI Calcined phosphate rock charged to digester pounds-. 2, 200 2, 140 P205 in calcined phosphate rock -.do 730 Y730 Phosphoric acid rccirculatcd to digester .do-.-- 16,000 22, 000 Digester temperature CC.. 60 75 Dig-ester time -.1 .honrs.-- 1 l Enlnent leaving digester and entering reactor Y' Y po 18, 200 24, 140 Sulfuric acid entering reactor .Y 146 Concentration of sulfuric aci -p 93. 15 Recirculated acid (H2804 an HrPOD entering reactor 5, 780 Reactor temperature. 60 75 Reactor time.; 2 2 Efluent leaving reactor and cntermD i ter v Y pounds.- 24, 800 30,066 Phosphoric acid product leaving system. .do.--. 2, 000 1, 666 H2O d0 890 560 d0 724 724 -..per cent-- 50 60 do--. 0.5 0.6

Table z-coritimiedY V VI Slurry leaving filter and entering converter pounds-- 6, 800 6, 400 Solids in slurry .d Sulfuric acid enterin do Concentration of sulfuric acid r cen 93.15 93. 22 Filtrate entering converter from subsequent filtration..Y .pounds-- 2, 100 2, 300 Eiiluent leaving converter and entering filter Y 10, 800 11, 500 Water for Washing calcium sulfate anhydrite 1,900 1,580 Prccipitate removed from lter --do---- 4, 000 4, 000 Composition of precipitate:

Solids do 2, 860 2, 848 CaS O4 in solids 2, 440 2, 500 H2 l, 140 1, 152 P2Ou-- --do---- 6 6 P205 loss in calcium sulfate anhydrite per cent-- 0.8 0.8

Although certain preferred embodiments of the invention have been disclosed for purposes of illustration, it will be evident that various changes and modifications may be made therein Without departing from the scope and spiritof the invention which is not to be limited save as defined in the appended claims.

We claim:

i. In a process for converting a calcium salt of phosphoric acid into phosphoric acid and a precipitate of calcium sulfate by reaction with sulfurie acid, the improvement which comprises separatinfg, the mixture of phosphoric acid and precipitate of calcium sulfate into a phosphoric acid portion substantially free from precipitate and a residue in the forni of a slurry containing calcium sulfate precipitate and a substantial amount of liquid phosphoric subjecting residue to the action of a sulfuric acid solution, maintaining the mixture of sulfuric acid solution and said residue for a sumcient length of time to convert the calcium sulfate precipitate to calcium sulfate Vanhydrite at temperatures Within the range of the boiling point of the sulfuric acid solution to 600 C., the temperature of the mixture being so correlated with the concentration of sulfuric acid `in the solution that at a temperature of the 'coiling point of the solution said solution contains at least 15% sulfuric acid with this minimum limit increasing to 33% for a mixture at 66 C., sepVA -arating said anhydrite from the liquor, andreturning said liduor to the caicium salt of phosphoric acid for further conversion into phosphoric acid and a precipitate of calcium sulfate.

2. In a process for converting a calcium salt of phosphoric acid into phosporic acid and a precipitate of calcium sulfate by reaction with sul- Vfurie acid, the improvement which comprises separating the mixture of phosphoric acid and precipitate of calcium sulfate into a phosphoric acid portion substantially free from precipitate and a residue in the form of a slurry containing calcium ysulfate precipitate and a substantial amount of liquid phosphoric acid, subjecting said residue to the action of a sulfuric acid solution, maintaining the mixture of sulfuric acid solution and said residue for a sufficient length of time to convert the calcium sulfate precipitate to calcium sulfate anhydrite at temperatures within the range of the boiling point of the sulfuric acid solution to C., the temperature of the mixture being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point of the solution said solution contains at least 15% sulfuric acid with this minimum limit increasing to 33% for a mixture at 60 C., introducing a small amount of calcium sulfate anhyassuma' drite seed .into said mixture thereby promoting the Iformation of ne-,particle calcium sulfate anhydrite, separating said anhydrite `'from the liquor, and returning Asaid liquor to the calcium salt of phosphoric acid for further conversion into phosphoric acid and a precipitate oi calcium sulfate.

3. A process for converting phosphatic material ,into phosphoric acid and calcium sulfate anhydrite which comprises digesting said phosphatic .material with phosphoric acid, adding sulfuric acid to the reaction products resulting from said digestion in an amount sufficient to convert the said reaction products into phosphoric `acid land a precipitate of calcium sulfate hydrate, separating the mixture of phosphoric acid and precipitate of calcium sulfate Vhydrate 'into a phosphoric acid portion substantially free from Iprecipitate and a residue in the form of a slurry vcontaining calcium sulfate hydrate and asubstantial `amount of liquid phosphoric acid, withdrawing a portion of said phosphoric acid substantially freefrom precipitate from the system, recirculating another portion of said phosphoric acid substantially free from precipitate to lsaid phosphatic material, adding a sulfuric acid solution to said residue, maintaining the mixture of sulfuric acid and said residue for a suficient length of time to convert the calcium sulfate hydrate to calcium sulfate anhydrite at temperatures Within the range of the boiling point of the sulfuric acid solution to 60 C., the temperature of `the mixture being .so correlated with the-concentration of sulfurie acid in the solution that at a temperature of .the boiling point of the solution said solution contains atleast sulfuric acid with this min im-um limit increasing to 33% fora mixture at 50 C., separating-calcium sul-fate anhydrite from the liquor and introducing said liquor into the reaction products for further conversion into phosphoric acid anda precipitate of calcium sulfate hydrate.

i. A process ,for converting phosphatic amate rial into phosphor-ic acid and calcium sulfate ranhydrite which comprises digesting said phosphatic material with phosphoric acid, adding sul- `furie acid to the reaction products ,resulting from said digestion in an .amount suflicient to convert said reaction products to phosphoric acid and a precipitate of calcium sulfate, separating the `mixture .of phosphoric acid and precipitate of calcium sulfate into phosphoric acid substantially free from precipitate constituting a major portion of the `phosphoric acid in the mixture and a residue in the form oi a slurry containing calcium sulfate precipitate and the remaining portion of liquid phosphoric acid constituting `a substantial part Aof the residue, withdrawing a portion of said phosphoric acid substantially free from precipitate from the system, recirculating another portion of said phosphoric acid substantially Afree from precipitate to the phosphatic material, adding sulfuric acid to said residue to effect conversion of insoluble phosphates to soluble phosphates and to transform `hydrated calcium sulfate into calcium sulfate anhydrite, introducing a` small amount of calcium sulfateanhydrite seed into the mixture of sulfuric acid and residue thereby promoting the formation of fine-particle calcium sulfa anhydrite, separating .calcium sulfate anhydrite `from the liquor and introducing said liquor into said reacn ton products for further conversion into phosphoric acid and a precipitate of calcium sulfate.

5. Aprocess for nverting phosphate rock into strong phosphoric acid and fineparticle calcium sulfate anhydrite which comprises digesting said phosphate `rock with phosphoric acid in an amount su'fcient to convert the calcium phosphate in said rock linto monocalcium phosphate dissolved in an excess of phosphoric acid, separating at least the coarse gangue from the mono- .calcium ,phosphate solution, adrnixing sulfuric acid with the ymonocalciuin phosphate solution in an amount sufcient to effect conversion of the monocalc'ium vphosphate solution into phosphoric acid and a vhydrated calcium sulfate precipitate, separating the mixture of phosphoric acid and hydrated calcium sulfate precipitate into a phosphoric acid portion substantially free from precipitate .and a residue in the 4lorm of a slur-ry containing hydrated calcium sulfate precipitate and a substantial amount o liquid phosphoric acid, withdrawing a minor portion of said phosphoric acid substantially free `'from `precipitate from the system, recirculating a major ,portion of said phosphoric acid substantially free .from precipitate to the .phosphate rock for further conversion into monocalciumphosphate, adding sulfuric acid to said residue to eiiec't conversion of insoluble phosphates to soluble phosphates and to transform the-calcium sulfate into calcium sulfate anhydrite, introducing a small amount o'f calcium sulfate anhydrite seed into the mixture of sulfuric acid and .said residue thereby promoting the formation `of line-particle calcium sulfate anhydrite, separating the calcium "sulfate anhydrite from the liquor and returning 'the liquor lto the monocalcium phosphate solution.

6. A process for converting .phosphatic material into strong phosphoric acid and calcium sulfate anhydrite which comprises digesting `said phosphatic material with phosphoric acid in an amount suflicient to convert the calcium phosphate in said phosphatic material into monocalcium phosphate dissolved in an excess of phosphoric acid, separating insoluble solids from the monocalcium phosphate solution, admixing sulfuric acid with the monocalcium phosphate solution in an amount sufcient to effect conversion of the monocalcium phosphate solution into phosphoric acid and a hydrated calcium sulfate precipitate, separating the mixture* of .phosphoric acid and hydrated calcium -sulfatepree cipitate into a phosphoric acid portion `substantially free from precipitate and a residue in the form of .a slurry containing hydrated calciumsulfate precipitate and a substantial amount of liquid phosphoric acid, withdrawing a portion o'f Vsaid phosphoric acid substantially free from precipitate from the system, .recirculating a portion of said phosphoric acid substantially Afree from precipitate for washing the separated ina soluble solids, recirculating a portion of said phosphoric acid substantially free from .precipitate to the phosphatic `material for further conversion into monocalcium phosphate, adding a sulfuric acid solution to said residue, maintaining the mixture of sulfur-ic acid and said residue for a suflicient length of time to convert insoluble phosphates to soluble phosphates and to transform the calcium sulfate hydrate into calcium sulfate anhydrite at temperatures within the range `of the boiling `point of the sulfuric acid solution to 60 C., the temperature of the mix- 'ture Vbeing so correlated 4with the concentration of sulfuric acid in the solution that at a temperavture ofthe boiling point ofthe solution said solution contains `at least 15% sulfuric acid with this minimum .limit increasing to 33% for a mixture at 60 C., separating the calcium sulfate anhydrite from the liquor, and returning the liquor to the monocalcium phosphate solution.

7. A process of making strong phosphoric acid and calcium sulfate anhydrite from phosphate rock and sulfuric acid which comprises calcining and grinding phosphate roclg'digesting said rock with 8 to v14 parts by weight of strong phosphoric acid produced. in the process for a sufcient length of time to convert the calcium phosphate in said rock to monocalcium phosphate, separating gangue from the monocalcium phosphate solution, washing the gangue with phosphoric acid produced in the process and with water,

combining said washings with the monocalciumV phosphate solution, adding sulfuric acid to the mixture of washings and monocalcium phosphate in an amount in slight excess ofY that theoretifcally required to convert the monocalcium phosphate into calcium sulfate hydrate precipitate, separating the mixture of phosphoric acid and hydrated calcium sulfate precipitate into a phosphoric acid portion substantially free from precipitate and a residue in the form of a slurry containing hydrated calcium sulfate precipitate and a substantial amount of liquid phosphoric acid, withdrawing a portion of said phosphoric acid substantially free from precipitate from the system, recirculating a major portion of the remaining phosphoric acid substantially free i from precipitate for digestion of the phosphate rock, recirculating a minor portion of the remaining phosphoric acid substantially free from precipitate for washing the gangue, adding a sulfuricy acid solution to a major portion of said residue, maintaining the mixture of sulfuric acid and said major portion of residue for a sufiicient length of time to convert insoluble phosphates to soluble phosphates and to transform calcium sulfate precipitate into stable calcium sulfate anhydrite at temperatures within the range of the boiling point of the sulfuric acid solution to 60 C., the temperature of the mixture being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point of the solution said solution contains at least 15% s1 lfuric acid with this minimum limit increasing to 33% for a mixture at 60 C., subjecting a minor portion of said residue to the action of strong sulfuric acid to produce thereby a calcium sulfate anhydrite seed, introducing said calcium sulfate anhydrite seed into the mixture of the major portion of said residue and sulfuric acid in an amount between 2% and 10% of the weight of the calcium sulfate of said residue thereby promoting the formation of a fine-particle calcium sulfate anhydrite, separating said calcium sulfate anhyn drite from the liquor, water washing said calcium sulfate anhydrite, combining said washing with said liquor, returning a portion of said liquor to the mixture of sulfuric acid solution and major portion of residue, and introducing the remaining liquor into the monocalcium phosphate solution for further conversion into phos phoric acid and a calcium sulfate precipitate.

8. A process for production of phosphoric acid which comprises mixing sulfuric acid and a caly cium salt of phosphoric acid thereby obtaining a mixture of phosphoric acid and a precipitate oi.

calcium sulfate, separating the mixture of phosphoric acid and 'precipitate vof calcium sulfate into a phosphoric acid portion substantially free from precipitate and a residue in the form of a slurry 'containing calcium sulfate precipitate and:

subjecting said residue to the action of sulfuric acid for a suiiicient length of time to convert the calcium sulfate precipitate into stable calcium sulfate anhydrite at temperatures within the range of the boiling point of sulfuric acid solution to C7 C., the temperature of the mixture being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point of the solution, said solution contains at least 1.5% sulfuric acid with this minimum limit increasing to 33% for a mixture at 60 C., separating the mixture of unconverted sulfuric acid and phosphoric acid from the stable calcium vsulfate anhydrite, and returning the mixture of unconverted sulfuric acid and phosphoric acid separated from the stable calcium sulfate anhydrite to said calcium salt of phosphoric acid for further conversion intophosphoric acid and a precipitate of calcium sulfate.

9. In a process for converting a calcium salt of phosphoric acid into phosphoric acid and a precipitate of calcium sulfate hydrate containing insoluble phosphates by reaction with sulfuric acid, the improvement which comprises separating themixture of phosphoric acid and precipitate of calcium sulfate hydrate into a phosphoric acid portion substantially free from precipitate and a residue in the form of a slurry containing calcium sulfate precipitate and a substantial' amount of liquid phosphoric acid, subjecting said residue to the action of sulfuric acid for a sufficient length of time to convert insoluble phosphates in the precipitate to soluble phosphates'and to transform the calcium sulfate precipitate into stable calcium sulfate anhydrite at temperatures within the range of the boiling point of sulfuric acid solution to 60 C., the temperature being so correlated with` the concentrad tion of sulfuric acid in the solution that at a temperature of the boiling point of the solution said solution contains at least 15% sulfuric acid with this limit increasing to 33% for a mixture at 50 C., separating the mixture of unconverted sulfuric acid and soluble phosphates from the calcium sulfate anhydrite and returning the mixture of unconverted sulfuric acid and soluble phosphates separated from the calcium sulfate anhydrite to said calcium salt of phosphoric acid for further conversion into phosphoric acid and a precipitate of calcium sulfate hydrate.

10. A process for converting phosphatic material into phosphoric acid and calcium sulfate which comprises digesting said phosphatic material with phosphoric acid, adding sulfuric acid to the reaction products resulting from said digestion in an amount slightly in excess of that theoretically required to convert the phosphatic material to phosphoric acid and a precipitate of calcium sulfate, separating the mixture of phosphoric acid and precipitate of calcium sulfate into a major portion of phosphoric acid substantially free from precipitate of calcium sulfate and a residue in the form of, a slurry containing calcium sulfate precipitate and the remaining portion of liquid phosphoric acid constituting a substantial part of the residue, withdrawing a portion of said phosphoric acid substantially free from precipitate from the system, recirculatinganother portion of said phosphoric acidsubstantially Vfree from precipitate to said phosphatic material, subjecting the said residue to the actionV of sulfuric acid for a suiicient length 'Qf time i@ convert insolume phosphates in the precipitate to soluble phosphates and to transform the calcium sulfate precipitate into calcium sulfate anhydrite at temperatures Within the range of the boiling point of sulfuric acid solution to 60 C., the temperature being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point of the solution, said solution contains at least 15% sulfuric acid with this minimum limit increasing to 33% for a mixture at 60 C., separating the calcium sulfate anhydrite from the liquor and introducing said liquor substantially free from calcium sulfate anhydrite into said reaction products for further conversion into phosphoric acid and a precipitate of calcium Sulfate.

ll. A process for converting phosphate rock into phosphoric acid and calcium sulfate anhydrite which comprises digesting said phosphate rock with suiiicient phosphoric acid to convert the calcium phosphate in the phosphate rock into a solution of monocalcium phosphate, adding sulfuric acid to the reaction products resulting from said digestion in an amount suiflcient to convert the monocalcium phosphate to phosphoric acid and a precipitate of calcium sulfate, separating the 4mixture of phosphoric acid and precipitate of calcium sulfate into phosphoric acid substantially free from precipitate and a residue in the form of a slurry containing calcium sulfate precipitate and a substantial amount of liquid phosphoric acid, withdrawing a portion of said phosphoric acid substantially free from precipitate from the system, recirculating another portion of said phosphoric acid substantially free from precipitate to the phosphate rock, subjecting said residue to the action of sulfuric acid for suliicient length of time to convert insoluble phosphates in the precipitate to soluble phosphates and to transform the calcium sulfate precipitate into stable calcium sulfate anhydrite at temperatures within the range of the boiling point of sulfuric acid solution to 60 C., the temperature of the mixture being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point said solution contains at least 15% sulfuric acid With this minimum limit increasing to 33% for a mixture at 60 C., separating the calcium sulfate anhydrite from the liquor and introducing said liquor substantially free from calcium sulfate anhydrite into the monocalcium phosphate solution for further conversion into phosphoric acid and a precipitate of calcium sulfate.

12. A process for converting phosphate rock into phosphoric acid and calcium sulfate anhydrite which comprises digesting said phosphate rock with phosphoric acid in an amount suiicient Vto convert the calcium sulfate in said phosphate rock into monocalcium phosphate dissolved in an excess of phosphoric acid, separating gangue from the monocalcium phosphate solution, admixing sulfuric acid with the monocalcium phosphate solution in an amount suiiicient to effect conversion of the monocalcium phosphate Solution into phosphoric acid and a calcium sulfate precipitate, separating the mixture of phosphoric acid and calcium sulfate precipitatelinto phosphoric acid substantially free from calcium sulfate precipitate constituting a major portion of the phosphoric acid in the mixture and a residue in the form of a slurry containing calcium sulfate precipitate and the remaining portion of liquid phosphoric acid constituting a substantial part of the residue, withdrawing a minor portion of said phosphoric acid substantially free from precipitate from the system, recirculating a major portion of said phosphoric acid substantially free from precipitate to the phosphate rock for further conversion into monocalcium phosphate, subjecting said residue to the action of sulfuric acid for a suflicient length of time to convert insoluble phosphates in the precipitate to soluble phosphates and to transform the calcium sulfate precipitate into stable calcium sulfate anhydrite at temperatures Within the range of the boiling point of sulfuric acid solution to C., the temperature of the mixture being so correlated with the concentration of sulfuric acid in the solution that at a temperature of the boiling point of the solution, said solution contains 15% sulfuric acid with this minimum limit increasing to 33% for a mixture at 60 C., separating the treated calcium sulfate precipitate from the liquor, and returning the liquor to the monocalcium phosphate solution.

BERNDT WALDEMAR HAMMAREN. ROBERT VOSE TOWNEND.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,776,595 Nordengren Sept. 23, 1930 2,002,547 Nordengren May 28,` 1935 2,006,342 Bouge et al July 2, 1935 2,049,032 Weber et al July 28 1936 2,485,164 Peirce Oct. 18, 1949 FOREIGN PATENTS Number Country Date 453,582 Great Britain Dec. 5, 1934 515,293 Great Britain Nov. 30, 1939 

1. IN A PROCESS OF CONVERTING A CALCIUM SALT OF PHOSPHORIC ACID INTO PHOSPHORIC ACID AND A PRECIPITATE OF CALCIUM SULFATE BY REACTION WITH SULFURIC ACID, THE IMPROVEMENT WHICH COMPRISES SEPLARATING THE MIXTURE OF PHOSPHORIC ACID AND PRECIPITATE OF CALCIUM SULFATE INTO A PHOSPHORIC ACID PORTION SUBSTANTIALLY FREE FROM PRECIPITATE AND A RESIDUE IN THE FORM OF A SLURRY CONTAINING CALCIUM SULFATE PRECIPITATE AND A SUBSTANTIAL AMOUNT OF LIQUID PHOSPHORIC ACID, SUBJECTING SAID RESIDUE TO THE ACTION OF A SULFURIC ACID SOLUTION, MAINTAINING THE MIXTURE OF SULFURIC ACID SOLUTION AND SAID RESIDUE FOR A SUFFICIENT LENGTH OF TIME TO CONVERT THE CALCIUM SULFATE PRECIPITATE TO CALCIUM SULFATE ANHYDRITE AT TEMPERATURES WITHIN THE RANGE OF THE BOILING POINT OF THE SULFURIC ACID SOLUTION TO 60*C., THE TEMPERATURE OFR THE MIXTURE BEING SO CORRELATED WITH THE CONCENTRATION OF SULFURIC ACID IN THE SOLUTION THAT AT A TEMPERATURE OF THE BOILING POINT OF THE SOLUTION SAID SOLUTION CONTAINS AT LEAST 15% SULFURIC ACID WITH THIS MINIMUM LIMIT INCREASING TO 33% FOR A MIXTURE AT 60*C., SEPARATING SAID ANHYDRITE FROM THE LIQUOR, AND RETURNING SAID LIQUOR TO THE CALCIUM SALT OF PHOSPHORIC ACID FOR FURTHER CONVERSION INTO PHOSPHORIC ACID AND A PRECIPITATE OF CALCIUM SULFATE. 